Abstract
In this thesis, copper complexes bearing bidentate, tridentate, and tetradentate N-ligands were synthesised and characterised. The ligands’ design draws inspiration from the histidine copper brace, a structural motif found in enzymes. The compounds were investigated, among other techniques, with nuclear magnetic resonance (NMR) spectroscopy and UV/Vis spectroscopy. A combination of Variable Temperature (VT) 1H NMR, Diffusion Ordered Spectroscopy (DOSY) and 1H-15N Heteronuclear Multiple-Bond Correlation (HMBC) allowed to study the aggregation behaviour of the compounds. Pyridine and imidazole bearing N,N,N,Ncopper( I) complexes both formed dimers, yet these dimers are of different constitution. 15N NMR coordination shifts were obtained for several copper(I) complexes, highlighting the interplay between imine and heterocycle. In UV/Vis experiments, the aggregation behaviour of a bispyridine copper(I) complex in solution led to deviation from the linear correlation between concentration and absorption given by the Lambert-Beer law. While exploring the synthetic scope of the protocol for the tetradentate ligands, the formation of dibenzo[d,f]-1,2- dihydro-[1,3]diazepines was observed. The formation of this side product was influenced by a delicate interplay of the substituents on the employed aldehyde and Lewis acidic reagents present in the reaction mixture. Additionally to the aforementioned copper complexes, two pentacoordinated salen-type copper(II) complexes were synthesised. Their ligands differ only by a nitro-substitution para to the oxygen binding copper, yet this had a strong effect on the coordination geometry around copper as seen by single crystal X-ray diffraction. The oxidation of a tetracoordinated bisimidazole copper(I) complex in acetonitrile solution upon air exposure was studied by UV/Vis spectroscopy. The majority of copper complexes were synthesised with the aim to incorporate them into metal organic frameworks. The incorporation was successfully shown for two of the complexes. Preliminary studies of the oxidation of the complexes and their catalytic performance suggest that the herein presented complexes are promising catalyst candidates for aliphatic C–H oxidation.
List of papers
Paper I: Structural Elucidation, Aggregation, and Dynamic Behaviour of N,N,N,N-Copper(I) Schiff Base Complexes in Solid and in Solution: a Combined NMR, X-ray Spectroscopic and Crystallographic Investigation. Isabelle Gerz, Sergio Augusto Venturinelli Jannuzzi, Knut T. Hylland, Chiara Negri, David S. Wragg, Sigurd Øien-Ødegaard, Mats Tilset, Unni Olsbye, Serena DeBeer, Mohamed Amedjkouh. Eur. J. Inorg. Chem. 2021, 4762-4775. The paper is included in the thesis in DUO, and also available at: https://doi.org/10.1002/ejic.202100722 |
Paper II: Enabling a Bioinspired N,N,N- Copper Coordination through Spatial Control in UiO-67: Synthesis and Reactivity towards H2O and O2. Isabelle Gerz, Erlend S. Aunan, Knut T. Hylland, Ning Cao, David S. Wragg, Ainara Nova, Mohamed Amedjkouh. Manuscript under preparation. To be published. The paper is removed from the thesis in DUO awaiting publishing. |
Paper III: Synthesis and Luminescence of Dibenzo[d,f]-1,2-dihydro-[1,3]diazepines. Isabelle Gerz, Rafael Cortez Sgroi Pupo, David S. Wragg, Ainara Nova, Mohamed Amedjkouh. Manuscript under preparation. To be published. The paper is removed from the thesis in DUO awaiting publishing. |
Paper IV: The Reactivity of Multidentate Schiff Base Ligands Derived from Bi- and Terphenyl Polyamines towards M(II) (M=Ni, Cu, Zn, Cd) and M(III) (M=Co, Y, Lu). Knut Tormodssønn Hylland, Isabelle Gerz, David S. Wragg, Sigurd Øien-Ødegaard, Mats Tilset. Eur. J. Inorg. Chem. 2021, 1869-1889. The paper is included in the thesis in DUO, and also available at: https://doi.org/10.1002/ejic.202100170 |